Investigating the formation and the properties of monoalkyl carbonates in aqueous medium using capillary electrophoresis with capacitively coupled contactless conductivity detection

Although alkyl carbonic acids (ACAs) and their salts are referred to as instable species in aqueous medium, we demonstrate that a monoalkyl carbonate (MAC) can in fact be easily formed from bicarbonate and an alcohol even in the presence of a high amount of water. A CE system with two capacitively coupled contactless conductivity detectors (C?Ds) was used to obtain different parameters about these species and their reactions. Based on the mobilities obtained for a series of alcohols ranging from 1 to 5 carbons, the coefficients of diffusion and the hydrodynamic radii were calculated. When compared with the equivalent carboxylates, MACs have radii systematically smaller. Although the precise pK(a) values of the ACAs could not be obtained, because of the fast decomposition in acid medium, it was possible, for the first time, to show that they are below 4.0. This result suggests that the acidity of an ACA is quite similar to the first hydrogen of H?CO?. Using a new approach to indirectly calibrate the C?D, the kinetic constants and the equilibrium constants of formation were also obtained. The results suggest that the increase in the chain length makes the MACs less stable and more inert.     

Buffers to suppress sodium dodecyl sulfate adsorption to polyethylene oxide for protein separation on capillary polymer electrophoresis

Although polyethylene oxide (PEO) offers several advantages as a sieving polymer in SDS capillary polymer electrophoresis (SDS-CPE), solution properties of PEO cause deterioration in the electrophoresis because PEO in solution aggregates itself, degrades into smaller pieces, and forms polymer-micelle complexes with SDS. We examined protein separation on SDS-CPE with PEO as a sieving matrix in four individual buffer solutions: Tris-CHES, Tris-Gly, Tris-Tricine, and Tris-HCl buffers. The solution properties of PEO as a sieving matrix in those buffers were examined by dynamic light scattering (DLS) and by surface tension. Preferential SDS adsorption onto PEO disturbed protein-SDS complexation and impaired the protein separation efficiency. Substantial adsorption of SDS to PEO was particularly observed in Tris-Gly buffer. The Tris-CHES buffer prevented SDS from adsorbing onto the PEO. Only Tris-CHES buffer achieved separation of six proteins. This study demonstrated efficient protein separation on SDS-CPE with PEO.     

Liquid crystal gels cross-linked with 1,3,5-tris-(ω-methacryloyloxyalkyloxy)benzenes

A mixture of ω-(4-cyanobiphenyl-4′-yloxy)alkyl methacrylate and 1,3,5-tris-(ω-methacryloyloxyalkyloxy)benzene was heated to 200 °C at 5–10 °C/min. A large, broad exothermic transition peak was observed by differential scanning calorimetry during the first heating process. The transition indicated the formation of a networked polymer, which was then immersed for 24 h in various nematic liquid crystals, such as 4-cyano-4′-pentylbiphenyl, to give liquid crystal gels. The networked polymers and their corresponding liquid crystal gels exhibited different liquid crystal-isotropic transitions. The swelling behaviors of the liquid crystal gels were compared with those of gels cross-linked with 1,6-hexanediol dimethacrylate, trimethylpropane trimethacrylate, and pentaerythritol tetraacetate. The characteristics of liquid crystal gels cross-linked with 1,3,5-tris-(ω-methacryloyloxyalkyloxy)benzenes were studied.     

Sequential injection immunoassay for environmental measurements

Sequential injection immunoassay systems for environmental measurements based on the selective immunoreaction between antigen and antibody were described. A sequential injection analysis (SIA) technique is suitable to be applied for the procedure of enzyme-linked immunosorbent assay (ELISA), because the washing and the addition of reagent solutions can be automated by using a computer-controlled syringe pump and switching valve. We selected vitellogenin (Vg), which is a biomarker for evaluating environmental risk caused by endocrine-disrupting chemicals in the hydrosphere, and linear alkylbenzene sulfonates (LAS) and alkylphenol polyethoxylates (APEO), which are versatile surfactants, as target analytes in the flow immunoassay systems. For Vg monitoring, SIA systems based on spectrophotometric, chemiluminescence, and electrochemical determinations were constructed. On the other hand, chemiluminescence determination was applied to the detection of LAS and APEO. For APEO, an SIA system combined with surface plasmon resonance (SPR) sensor was also developed. These new sequential injection immunoassay systems are expected to be useful systems for environmental analysis.     

Synthesis of stereoarray isotope labeled (SAIL) lysine via the "head-to-tail" conversion of SAIL glutamic acid

A stereoarray isotope labeled (SAIL) lysine, (2S,3R,4R,5S,6R)-[3,4,5,6-(2)H(4);1,2,3,4,5,6-(13)C(6);2,6-(15)N(2)]lysine, was synthesized by the "head-to-tail" conversion of SAIL-Glu, (2S,3S,4R)-[3,4-(2)H(2);1,2,3,4,5-(13)C(5);2-(15)N]glutamic acid, with high stereospecificities for all five chiral centers. With the SAIL-Lys in hand, the unambiguous simultaneous stereospecific assignments were able to be established for each of the prochiral protons within the four methylene groups of the Lys side chains in proteins.     

Enantioselective total synthesis of the potent anti-HIV nucleoside EFdA

A concise enantioselective total synthesis of 4'-ethynyl-2-fluoro-2'-deoxyadenosine (EFdA), an extremely potent anti-HIV agent, has been accomplished from (R)-glyceraldehyde acetonide in 18% overall yield by a 12-step sequence involving a highly diastereoselective ethynylation of an α-alkoxy ketone intermediate.     

Monitoring the aggregation processes of amyloid-β using a spin-labeled, fluorescent nitroxyl radical

Amyloid nitroxyl radical (nitroxide) ligands were used to detect amyloid-β fibrils, the main constituents of senile plaques in Alzheimer's disease, using anisotropic ESR spectra, and were found to affect the aggregation process due to the radical functionality. These compounds have great potential as novel and multifunctional probes, combining spin labels, spin probes, and fluorescence probes.     

Highly efficient enzymatic synthesis of 3'-deoxyapionucleic acid (apioNA) having the four natural nucleobases

The synthesis of the 3'-deoxyapionucleoside 3'-triphosphates (apioNTPs) having the four natural nucleobases and their enzymatic incorporation into a DNA-DNA primer-template have been tried. Therminator DNA polymerase was shown to incorporate these apioNTPs effectively giving 43mer DNA-apioNA chimera.     

Differences in the yields of polycyclic aromatic hydrocarbons by pressurized liquid extraction and the Japanese official method

To improve the extraction of polycyclic aromatic hydrocarbons (PAHs) from sediment samples, we optimized the conditions of pressurized liquid extraction (PLE). The yields increased as the extraction temperature increased from 100 to 190 degrees C, but the effect of increasing pressure (from 15 to 20 MPa) was small. Parameters of 190 degrees C and 20 MPa, near the maximum of the equipment, gave the highest yield. Under these conditions, the yields of 17 PAHs were 1.5 - 34 times those obtained by the Japanese official method (shaking and ultrasonic extraction with acetone at room temperature).     

Determination of peptide φ angles in solids by relayed anisotropy correlation NMR

A solid state NMR method is presented for determination of a backbone dihedral angle φ in peptides, being based on the previously reported method, relayed anisotropy correlation (RACO) NMR [Y. Ishii et al., Chem. Phys. Lett. 256 (1996) 133]. In the present method, the and the dipolar tensors in the system are two-dimensionally (2D) correlated via polarization transfer from to under magic angle spinning (MAS). This method was applied to N-acetyl , -valine, and the H–C–N–H dihedral angle was determined to be 154.0±1.4° or 206.0±1.4°, the former agreeing with the X-ray value of 154±5°.